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CN101210151A - Method for coating metal strip - Google Patents

Method for coating metal strip Download PDF

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Publication number
CN101210151A
CN101210151A CNA2007103059420A CN200710305942A CN101210151A CN 101210151 A CN101210151 A CN 101210151A CN A2007103059420 A CNA2007103059420 A CN A2007103059420A CN 200710305942 A CN200710305942 A CN 200710305942A CN 101210151 A CN101210151 A CN 101210151A
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CN
China
Prior art keywords
acid
agent
metal strip
coating
purposes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2007103059420A
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Chinese (zh)
Other versions
CN101210151B (en
Inventor
R·科沙贝克
M·巴特曼
T·布兰德
A·舒伯特
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Evonik Operations GmbH
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Degussa GmbH
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Publication of CN101210151A publication Critical patent/CN101210151A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to the use of branched amorphous macro-polyols based on polyester for the coating of metal bands, to a method for coating metal bands, and to the coated metal bands obtained in this way. The coating comprises branched polyesters having a content of tri-functional branchers of between 10 and 25 mol-%, based on the alcohol component, the molecular weight of the polyester is between 2500 and 4500 g/mol.

Description

The method of coating metal strip
Technical field
The present invention relates to be used for the purposes of coating metal strip, the method for coating metal strip and resulting thus sheet metal strip through applying based on the side chain amorphous macromole polyol of polyester.
Background technology
The coating of sheet metal strip also promptly applies a high-quality coating economically in order in very short time on the sheet metal strip such as the coiling that is made from aluminum or steel.Than other coating method, for example spraying, this method has significant advantage.For example this can be higher productivity and the phenomenon of dispersing seldom obtain high-quality uniform coating.
The coating of sheet metal strip is a kind of continuation method.In order to guarantee also to proceed at the terminal coating procedure of sheet metal strip, will use so-called collector, from this collector, can further in the limited time, infeed band laying in the time of next sheet metal strip.Usually want prior clean metal band, its pre-treatment and two sides are all imposed priming paint.
For coating metal strip uses the coating agent of liquid heating curable, it is made of the binding agent of hydroxyl such as polyester and end capped polyisocyanates and/or melamine resin and their derivative formed solution in organic solvent.As other compositions, that is worth mentioning has pigment and other additives.
More vital performances are for example weathering resistance, hydrolytic resistance, chemical-resistant reagent and scratch resistance, high glossiness, hardness and suppleness for the coating of sheet metal strip.Add man-hour when base material experiences one or more forming steps after the japanning process as deep-draw all very necessary for many parts, the latter can have influence on the adhesivity of coating strongly.
Weathering resistance at first will experience the parts of direct solar radiation and other weather effects for those surfaces, be vital, and the parts that belong to this type of have such as traffic sign, metope element, garage door, rainwater pipe and trolley part etc.
Generally speaking, if use softer and more flexible binding agent then the base material adhesivity can be better, on the other hand, then weathering resistance and work-ing life are better when adopting harder binding agent.
Except all these performances, it is significantly important to also have a factor also to play a part when coating metal strip, i.e. economy.Therefore people expect to apply long as far as possible sheet metal strip very much in time per unit.And the residence time or the required furnace temperature of sheet metal strip in stove also is limited size, so that realize that painted is crosslinked fully.Well known in the artly be, the molar mass of used polymkeric substance is more little, and the density that promptly has the group of crosslinked ability such as hydroxyl is high more, and then the residing time in furnace of the tinsel that so applies shortens, and promptly the crosslinking activity of used binding agent will raise.But, arbitrarily reduce molecular weight and the high crosslink density that brings thus can to cause a kind of the coating for sheet metal strip be the phenomenon of unacceptable final japanning embrittlement, particularly when using melamine compound as linking agent.
Equally, also can realize the shortening of roasting time by the raising furnace temperature.Except the higher energy expenditure of bringing thus of not expecting, can not at random realize high temperature for many base materials.For example so-called BH steel (" baking hardening ") can harden under comparatively high temps and also just can not form step again owing to this reason.
In order to guarantee the performance requriements of economy and japanning quality aspect, prior art (WO2004/039902) adopted a kind of by the side chain lower molecular weight binding agent and be used for the higher molecular weight of pliable and toughization and mainly be the mixture that the binding agent of straight chain is formed with linking agent, be used for coating metal strip.Utilize this ingredients just can guarantee that japanning has sufficiently high crosslinking activity in stove.
Based on a kind of japanning ingredients of binding agent, this two kinds of different binding agents and also will be mixed with the necessity that is coated with lacquer formulations with proper ratio at last of must preparing have just become obvious uneconomic synonym than only.
For these reasons, task of the present invention is to develop a kind of coating method and coating of sheet metal strip, it can bring those above-mentioned japanning performances and sufficiently high crosslinking activity is provided simultaneously, thereby can realize as far as possible little residing time in furnace under the situation of medium cross-linked dosage.
Usually the crosslinking activity that is known that the end capped polyester of OH-can increase along with the increase of OH number.But the polyester that to have high OH number be small molecular weight but can bring brittle japanning, and this japanning is because lacking toughness and can not be used for coating metal strip.
Now be surprised to find, contain trifunctional branching agent and the branched polyesters of its molecular weight between 2500 to 4500g/mol, for the coating of sheet metal strip, between high crosslinking activity and snappiness, have enough Harmony in pure composition 10 to 25mol%.This class branched polyesters is documented among the EP1479709.
Summary of the invention
Therefore, content of the present invention is to be used for based on the side chain amorphous macromole polyol of polyester the purposes of coating metal strip, wherein said compound by the carboxylic acid composition with obtain existing to react under the situation of cross-linking reagent by at least a pure composition of forming with respect to the alcohol of the trifunctional at least of pure composition meter 10 to 25mol% and 75 to 90mol% another kind of at least alcohol, wherein this polyester has
The M of 2500-4500g/mol n,
The OH value of 0-200mg KOH/g and
The acid number of 0 to 10mg KOH/g.
The used amorphous branched macromolecule polyol based on polyester of the present invention contains at least a aromatics and/or aliphatic dicarboxylic acid and/or the poly carboxylic acid as the initial acid composition, as phthalic acid, m-phthalic acid, terephthalic acid, alicyclic 1, the 2-dicarboxylic acid is as 1,2-cyclohexane diacid and/or methyl tetrahydrophthalic acid, tetrahydrophthalic acid and/or methylhexahydrophthaacid acid, succsinic acid, sebacic acid, undecane diacid, dodecanedioic acid, hexanodioic acid, nonane diacid, pyromellitic acid, trimesic acid, different n-nonanoic acid and/or dimer (fatty acid) yl.M-phthalic acid, 1 preferably, 2-cyclohexane diacid, phthalic acid and hexanodioic acid.
Each sour composition can be partially or completely by acid anhydrides and/or low-molecular-weight alkyl ester, and preferred methyl esters and/or ethyl ester are formed.
As the pure composition of trifunctional at least, can adopt for example TriMethylolPropane(TMP), trimethylolethane, 1,2,6-trihydroxy-six tetrahydroxybutanes, glycerine, trihydroxy-ethyl chlorinated isocyanurates, tetramethylolmethane, sorbyl alcohol, Xylitol and/or N.F,USP MANNITOL, and its amount is 10 to 25mol%, in pure composition.
In addition, pure composition can also contain the glycol and/or the polyvalent alcohol of other straight chains and/or side chain, aliphatic and/or alicyclic and/or aromatics.Be ethylene glycol, 1 preferably as other alcohol, 2-and/or 1, ammediol, glycol ether, dipropylene glycol, triglycol, Tetraglycol 99,1,2-and/or 1,4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1,3-methyl propanediol, 1,5-pentanediol, dihydroxyphenyl propane, B, C, F, norbornylene glycol, 1,4-benzyl dimethanol and 1,4-benzyl di-alcohol, 2,4-dimethyl-2-ethyl-1,3-hexylene glycol, cyclohexyl dimethanol, Dicidol, hexylene glycol, neopentyl glycol, and its amount is 75 to 90mol%, in pure composition.
Preferred acid is for example 1,2-cyclohexane diacid, phthalic acid and/or hexanodioic acid, and particularly following composition:
1 of 92-100mol%, the phthalic acid of 2-cyclohexane diacid and 0-8mol% and/or hexanodioic acid or
The phthalic acid of 60-70mol% and the hexanodioic acid of 30-40mol%.
Preferred glycol is an ethylene glycol (0-40mol%), 2 for example, 2 '-dimethyl-1, ammediol (35-80mol%), 1,6-hexylene glycol (0-15mol%), TriMethylolPropane(TMP) (10-25mol%).
Side chain amorphous macromole polyol can have less than 15.0mg KOH/g, preferably less than 10.0, the acid number ethyl-10 of preferred especially 0 to 5mg KOH/g is to the hydroxyl value of 200mg KOH/g, preferred 10 to 150, preferred especially 30 to 100mg KOH/g.
The number-average molecular weight M of gained nBe 2500 to 4500g/mol, preferred 3000 to 4000.
Acid number is determined according to DIN EN ISO 2114.
It is the amount of the potassium hydroxide represented with mg that so-called acid number (SZ) is interpreted as, and it is to be contained in sour needed amount in the gram material for neutralization.Testing sample is dissolved in the methylene dichloride and with the potassium hydroxide methanol solution potentiometric titration of 0.1N.
Hydroxyl value is determined according to DIN 53240-2.
In the method, sample and acetic anhydride are reacted under the condition of existence as the 4-dimethylaminopyridine of catalyzer, hydroxyl can acetylize in this process.And, can form the acetic acid of a part for each hydroxyl, and excessive acetic anhydride is followed hydrolysis bimolecular acetic acid is provided.The consumption of acetic acid is determined by the difference between main value and the blank value that carries out simultaneously with volumetry.
Utilize gel permeation chromatography (GPC) to determine molecular weight.In as the tetrahydrofuran (THF) of elutriant, characterize sample according to DIN 55672-1.
M n(UV)=and number-average molecular weight (GPC, UV-surveys), represent with g/mol
M w(UV)=and weight-average molecular weight (GPC, UV-surveys), represent with g/mol
The sheet metal strip through applying of gained of the present invention shows good performance, and particularly the test value of (T shape-bending) coating is≤2.0 in T shape-pliability test.
Embodiment
Content of the present invention is to be used for based on the side chain amorphous macromole polyol of polyester the purposes of coating metal strip.Used coating agent has following feature:
It contains a kind of side chain amorphous macromole polyol based on polyester, and this compound reacts under the cross-linking reagent existence condition by at least a carboxylic acid composition and at least a pure composition and obtains,
Wherein said carboxylic acid composition is selected from aromatics and/or aliphatic dicarboxylic acid and/or poly carboxylic acid, as phthalic acid, m-phthalic acid, terephthalic acid, the alicyclic dicarboxylic acid is as 1,2-, 1,3-, 1,4-cyclohexane diacid and/or methyl tetrahydrophthalic acid, tetrahydrophthalic acid and/or methylhexahydrophthaacid acid, succsinic acid, sebacic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, undecane diacid, pyromellitic acid, trimesic acid, different n-nonanoic acid and/or dimer (fatty acid) yl, preferred m-phthalic acid, 1,2-cyclohexane diacid, phthalic acid and/or hexanodioic acid
And described pure composition is made up of following:
1) alcohol of 10 to 25mol% trifunctional at least and
2) 75 to 90mol% another kind of at least glycol,
It is characterized in that,
The M of 2500-4500g/mol n,
The OH value of 0-200mg KOH/g, preferred 20-150mg KOH/g and preferred especially 30-100mgKOH/g and
The acid number of 0 to 10mg KOH/g, preferred 0-15mg KOH/g and preferred especially 0-5mg KOH/g.
Cross-linking reagent is for example polyisocyanates and/or melamine resin and/or their derivative.
In addition, amorphous macromole polyol based on polyester during coating can also use together with auxiliary agent and additive, particularly inhibitor, water and/or organic solvent, neutralizing agent, surfactant, oxygen trapping agent and/or free radical scavenger, catalyzer, preventing light agent, color brightening agent, photosensitizers, thixotropic agent, anti wrinkling agent, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, inner pattern releasing agent applicable, filler and/or the whipping agent in all composition 0 to 70 weight %.
Do not exist the metal in the restriction, particularly sheet metal strip to be selected from the one group of material that includes aluminium, steel and zinc for metal to be coated.
Equally, content of the present invention also is a kind of method of coating metal strip, coating material wherein is made up of the side chain amorphous macromole polyol based on polyester, this compound by at least a carboxylic acid composition with obtain existing to react under the situation of cross-linking reagent by at least a pure composition of forming with respect to the alcohol of the trifunctional at least of pure composition meter 10 to 25mol% and 75 to 90mol% another kind of at least alcohol, wherein this polyester has
The M of 2500-4500g/mol n,
The OH value of 0-200mg KOH/g and
The acid number of 0 to 10mg KOH/g,
Wherein, (curing the coating material on the sheet metal strip under the stoving temperature of maximum metal temperature=PMT) less than 220 ℃.
The observed value of the sheet metal strip coating that obtains thus in T shape-crooked test (T shape-bending) is≤2.0.
The used side chain amorphous macromole polyol based on polyester of the present invention can be according to currently known methods (referring to Dr.P.Oldring, Resins for Surface Coating, III rolls up, is published by SitaTechnology, 203 Gardiness House, Bromhill Road, London SW184JQ, England 1987), make by a step or the multistep esterification process of (partly) continuous or discrete initial acid and initial alcohol.
Preferably under 150 to 270 ℃, more preferably 180 to 260 ℃, preferred especially 200 to 250 ℃ temperature in inert atmosphere the used amorphous macromole polyol of preparation the present invention based on polyester.Can use nitrogen or rare gas, particularly nitrogen as rare gas element.Rare gas element has less than 50ppm, special oxygen level less than 20ppm.After the water decomposition of most Theoretical Calculation amount, can handle in a vacuum.Optional can also closing reaction with quicken to contract (gather) and/or pull under the condition of agent with separating reaction and operate adding catalyzer.Typical catalyzer is organic titanium or organo-tin compound, as tetrabutyl titanate ester or Dibutyltin oxide.Catalyzer can be chosen wantonly and add with other raw materials when reaction is initial or add after a while when reaction.That use as the towing agent can be the SolventNaphtha of toluene or various qualities for example
Content of the present invention also is the sheet metal strip that applies according to the present invention, the latter can use arbitrarily in the mode known to the technician, especially in construction and the construction industry (for example indoor application, roof, wall), is used for transport trade, family expenses and be used for further processing are as punching press or punching.
Bright even without more speaking more, therefrom also can know by inference, the technician can utilize above-mentioned these description in widest range.Therefore, be as illustrative preferred embodiment, and be in any way content to be limited anything but with embodiment.
Followingly at large set forth the present invention according to embodiment.Alternate embodiments more of the present invention can obtain similarly.
Embodiment 1
Mol％ Weight % Raw material
The acid composition
100 ?59.9 1,2-cyclohexyl dicarboxylic acid acid anhydride
100 Acid composition summation
The alcohol composition
30 ?7.5 Neopentyl glycol
39 ?10.3 Monoethylene glycol
15 ?13.2 1, the 6-hexylene glycol
16 ?9.1 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, in nitrogen atmosphere, make 59.9 parts 1,2-cyclohexyl dicarboxylic acid acid anhydride and 7.5 parts of neopentyl glycol, 10.3 parts monoethylene glycol, 13.2 parts 1, the TriMethylolPropane(TMP) reaction of 6-hexylene glycol and 9.1 parts is lower than 1mg KOH/g and hydroxyl value reaches 55 KOH/g until acid number.After the cooling polyester is dissolved in Solvesso with 65% In 150/ butyleneglycol (3: 1).
The analytical characteristic value:
OHZ＝55mg?KOH·g -1，SZ＝0.4mg?KOH·g -1，M n＝3600g·mol -1
Embodiment 2
Mol％ Weight % Raw material
The acid composition
100 55.2 1,2-cyclohexyl dicarboxylic acid acid anhydride
100 Acid composition summation
The alcohol composition
77.5 32.6 Neopentyl glycol
22.5 12.2 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, in nitrogen atmosphere, make 55.2 parts 1, it is 5mg KOH/g that the TriMethylolPropane(TMP) of 2-cyclohexyl dicarboxylic acid acid anhydride and 32.6 parts of neopentyl glycol and 12.2 parts reacts until acid number.After the cooling polyester is dissolved in Solvesso with 65% In 150/ butyleneglycol (3: 1).
The analytical characteristic value:
OHZ＝95mg?KOH·g -1，SZ＝5mg?KOH·g -1，M n＝2500g·mol -1
Embodiment 3
Mol％ Weight % Raw material
The acid composition
70 34.6 Phthalic acid
30 15.1 Hexanodioic acid
100 Acid composition summation
The alcohol composition
60.0 30.2 Neopentyl glycol
25 12.5 Monoethylene glycol
10 7.6 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, 34.6 parts phthalic acid and 15.1 parts of hexanodioic acids and 30.2 parts neopentyl glycol, 12.5 parts of monoethylene glycols and 7.6 parts of TriMethylolPropane(TMP)s are reacted until acid number be lower than 1mg KOH/g and hydroxyl value reaches 35 KOH/g.After the cooling polyester is dissolved in Solvesso with 65% In 150/ butyleneglycol (3: 1).
The analytical characteristic value:
OHZ＝35mg?KOH·g -1，SZ＝0.6mg?KOH·g -1，M n＝4100g·mol -1
The comparative example A
Mol％ Weight % Raw material
The acid composition
100 50 1,2-cyclohexyl dicarboxylic acid acid anhydride
100 Acid composition summation
The alcohol composition
97.5 48.8 Neopentyl glycol
2.5 1.2 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, in nitrogen atmosphere, make 50 parts 1, the TriMethylolPropane(TMP) of 2-cyclohexyl dicarboxylic acid acid anhydride and 48.8 parts of neopentyl glycol and 1.2 parts reacts until acid number and is lower than 5mg KOH/g and hydroxyl value is 47mg KOH/g.After the cooling polyester is dissolved in Solvesso with 65% In 100.
The analytical characteristic value:
OHZ＝47mg?KOH·g -1，SZ＝4.0mg?KOH·g -1，M n＝2100g·mol -1
Comparative Examples B
Mol％ Weight % Raw material
The acid composition
100 ?53.5 1,2-cyclohexyl dicarboxylic acid acid anhydride
100 Acid composition summation
The alcohol composition
77.5 ?38.8 Neopentyl glycol
22.5 ?12.7 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, in nitrogen atmosphere, make 53.5 parts 1, it is that 5mg KOH/g and hydroxyl value are 128mg KOH/g that the TriMethylolPropane(TMP) of 2-cyclohexyl dicarboxylic acid acid anhydride and 33.8 parts of neopentyl glycol and 12.7 parts reacts until acid number.After the cooling polyester is dissolved in Solvesso with 65% In 150/ butyleneglycol (3: 1).
The analytical characteristic value:
OHZ＝128mg?KOH·g -1，SZ＝50mg?KOH·g -1，M n＝2400g·mol -1
Comparative Examples C
Mol％ Weight % Raw material
The acid composition
100 50 1,2-cyclohexyl dicarboxylic acid acid anhydride
100 Acid composition summation
The alcohol composition
74 36.8 Neopentyl glycol
26 13.2 TriMethylolPropane(TMP)
100 Alcohol composition summation
Under maximum 250 ℃ temperature, in nitrogen atmosphere, make 50 parts 1, it is that 5mg KOH/g and hydroxyl value are 110mg KOH/g that the TriMethylolPropane(TMP) of 2-cyclohexyl dicarboxylic acid acid anhydride and 36.8 parts of neopentyl glycol and 13.2 parts reacts until acid number.After the cooling polyester is dissolved in Solvesso with 65% In 100.
The analytical characteristic value:
OHZ＝110mg?KOH·g -1，SZ＝5.1mg?KOH·g -1，M n＝2200g·mol -1
The japanning ingredients
Umber
65% polyester liquid 43.8
TiO 22310 31.7
Hexamethoxy methyl cyanuramide 1 7.5
Tosic acid 2 0.4
Flow promotor 3 0.8
The butyleneglycol acetic ester 8.6
DBE 7.2
1The Cymel 303 of Cytec Industries Inc. for example; The characteristics of this linking agent are its active NH 2-group is sealed by methoxyl group, and this methoxyl group can decompose again under the common comparatively high temps in the coiled material cladding process and can cause reaction with polyester.
2King Industries for example, the Nacure 2500 of Inc.; This an acidic catalyst (chemical end-blocking) is necessary, in order to realize the reaction between melamine composition and the polyester composition.
3The Byk 350 of Byk-Chemie for example; Flow and raising glossy acrylate additive in order to improve.This additive is given the long spray trace of japanning and is avoided indenture.Surface tension reduces very little; Do not influence paintability and middle layer cohesiveness.
Japanning detects
Japanning embodiment 1 Japanning embodiment 2 Japanning embodiment 3 The japanning comparative example A Japanning Comparative Examples B Japanning Comparative Examples C
?MEK 1Two-stroke ＞100 ＞100 ＞100 ＞100 ＞100 ＞100
?PMT 2[℃] 209 216 188 232 209 204
The bending of T shape 3 1.5 1.5 1.0 1.0 3.0 3.0
Method:
1 these testing method of ECCA testing method T11:(can be implemented in the basic crosslinked situation of curing detection of active japanning system under the condition.
Process:
Make aluminum or zinc-plated steel " paillon foil " be subjected to the chemical/physical effect with impregnated in cotton pad in the methylethylketone (MEK) (have 1 or 2kg weight (MEK-Hammer)) through applying.This effect is linear two-stroke, wherein can produce the chemical erosion effect to coating.Usually, the coating after the completely solidified should be able to tolerate 100 two-strokes (DH) injury-freely.For abundant solidified situation, then after first time two-stroke, in the time of suitably after a while (＜100DH) can dissolve japanning.Describe the two-stroke number that should be able to reach mutually with integer, and this also is for example for thorough state of cure or the cross-linking density or an active module of japanning system.)
2 maximum metal temperature (PMT) (maximum temperature values that in the process of curing, on foil surfaces, records)
3 ECCA testing method T5: the purpose of this operation is to estimate the ductibility and the cohesive strength of coating when being subjected to bending.Resistance value when determining 180 ° of bendings with the minimum bend radius that allows the sample generation not have the bending of tearing.
Process:
T shape-the bending of the sample that test is acted on
Sample disc must smooth and not distortion (for example gauffer).
Sample strip is bent in advance according to the outside direction of coating by means of faldstool with hand.
For this reason, be inserted in the minimum possible slit of faldstool according to the direction paillon foil that maximum 10cm is wide after the japanning side direction.
Then, at full tilt the paillon foil that pre-folds is pressed together in bench vice, making does not have the air seam.
Take on the bending that the magnifying glass that amplifies ten times is observed on the crack.
Then, on the width of whole bending shoulder, firmly stick a Tesafilmstreifen, throw off and observe adherent japanning particle rapidly.
Calculating paint film does not have crack (T shape-bending crack) or do not have to paint the minimum bend radius (0T-0.5T-1T etc.) of (T shape-bending-adhesion) of coming off on Tesafilm.

Claims (16)

1. the purposes that is used for coating metal strip based on the side chain amorphous macromole polyol of polyester, wherein said polyol by at least a carboxylic acid composition with obtain existing to react under the situation of cross-linking reagent by at least a pure composition of forming with respect to the alcohol of the trifunctional at least of pure composition meter 10 to 25mol% and 75 to 90mol% another kind of at least alcohol, wherein this polyester has:
The M of 2500-4500g/mol n,
The OH value of 0-200mg KOH/g and
The acid number of 0 to 10mg KOH/g.
2. the purposes of claim 1 is characterized in that, at least a carboxylic acid composition is selected from aromatics and/or aliphatic dicarboxylic acid and/or poly carboxylic acid.
3. claim 1 or 2 purposes, it is characterized in that, the carboxylic acid composition is phthalic acid, m-phthalic acid, terephthalic acid, the alicyclic dicarboxylic acid is as 1,2-, 1,3-, 1,4-cyclohexane diacid and/or methyl tetrahydrophthalic acid, tetrahydrophthalic acid and/or methylhexahydrophthaacid acid, succsinic acid, sebacic acid, undecane diacid, dodecanedioic acid, hexanodioic acid, nonane diacid, pyromellitic acid, trimesic acid, different n-nonanoic acid and/or dimer (fatty acid) yl, preferred m-phthalic acid, 1,2-cyclohexane diacid, phthalic acid and/or hexanodioic acid.
4. one or multinomial purposes in the claim 1 to 3, it is characterized in that, pure composition as trifunctional, use TriMethylolPropane(TMP), trimethylolethane, 1,2,6-trihydroxy-six tetrahydroxybutanes, glycerine, trihydroxy-ethyl chlorinated isocyanurates, tetramethylolmethane, sorbyl alcohol, Xylitol and/or N.F,USP MANNITOL.
5. one or multinomial purposes in the claim 1 to 4 is characterized in that, use the glycol and/or the polyvalent alcohol of aliphatic and/or alicyclic and/or the aromatics of straight chain and/or side chain as other pure compositions.
6. the purposes of claim 5 is characterized in that, other pure composition is selected from ethylene glycol, 1,2-and/or 1, ammediol, glycol ether, dipropylene glycol, triglycol, Tetraglycol 99,1,2-and/or 1,4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1,3-methyl propanediol, 1,5-pentanediol, dihydroxyphenyl propane, B, C, F, norbornylene glycol, 1,4-benzyl dimethanol and 1,4-benzyl di-alcohol, 2,4-dimethyl-2-ethyl-1,3-hexylene glycol, cyclohexanedimethanol, Dicidol, hexylene glycol.
7. one or multinomial purposes in the claim 1 to 6 is characterized in that, use polyisocyanates and/or melamine resin and/or their derivative as cross-linking reagent.
8. one or multinomial purposes in the claim 1 to 7 is characterized in that, the coating of the sheet metal strip that obtains the thus test value that (bending of T shape) obtains in T shape bending test is≤2.0.
9. one or multinomial purposes in the claim 1 to 8 is characterized in that, use with auxiliary agent and additive based on the side chain amorphous macromole polyol of polyester.
10. the purposes of claim 9, it is characterized in that auxiliary agent and additive are selected from inhibitor, water and/or organic solvent, neutralizing agent, surfactant, oxygen trapping agent and/or free radical scavenger, catalyzer, preventing light agent, color brightening agent, photosensitizers, thixotropic agent, anti wrinkling agent, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, inner pattern releasing agent applicable, filler and/or whipping agent.
11. one or multinomial purposes is characterized in that in the claim 1 to 10, the metal in the sheet metal strip is selected from aluminium, steel and zinc.
12. the method for a coating metal strip, coating material wherein is made up of the side chain amorphous macromole polyol based on polyester, the latter by at least a carboxylic acid composition with obtain existing to react under the situation of cross-linking reagent by at least a pure composition of forming with respect to the alcohol of the trifunctional at least of pure composition meter 10 to 25mol% and 75 to 90mol% another kind of at least alcohol, wherein said polyester has:
The M of 2500-4500g/mol n,
The OH value of 0-200mg KOH/g and
The acid number of 0 to 10mg KOH/g,
Wherein, under stoving temperature, cure coating material on the sheet metal strip less than 220 ℃ (PMT).
13. the method for claim 12 is characterized in that, the coating of the sheet metal strip that obtains the thus test value that (bending of T shape) obtains in T shape bending test is≤2.0.
14. the method for claim 12 or 13 is characterized in that, uses other auxiliary agents and the additive of maximum 70 weight %.
15. the method for claim 14, it is characterized in that auxiliary agent and additive are selected from inhibitor, water and/or organic solvent, neutralizing agent, surfactant, oxygen trapping agent and/or free radical scavenger, catalyzer, preventing light agent, color brightening agent, photosensitizers, thixotropic agent, anti wrinkling agent, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, inner pattern releasing agent applicable, filler and/or whipping agent.
16. the sheet metal strip through applying, it obtains according to one or multinomial described method in the claim 12 to 15.
CN200710305942.0A 2006-12-29 2007-12-28 method for coating metal strip Expired - Fee Related CN101210151B (en)

Applications Claiming Priority (2)

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DE200610062041 DE102006062041A1 (en) 2006-12-29 2006-12-29 Coating metal tape, e.g. for cladding or vehicle parts, involves using coating material containing amorphous, branched macro-polyester-polyol and crosslinker and then stoving at moderate temperature
DE102006062041.0 2006-12-29

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CN102229276A (en) * 2011-04-20 2011-11-02 镇江市万源电子有限公司 Aluminum strip with insulation coatings
CN102264834A (en) * 2009-04-14 2011-11-30 巴斯福涂料股份有限公司 water-based paint composition
CN103980449A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 Composite material for 3D printing and preparation method thereof
CN108084391A (en) * 2016-11-21 2018-05-29 航天特种材料及工艺技术研究所 A kind of polyurethane and preparation method thereof

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CN102264834A (en) * 2009-04-14 2011-11-30 巴斯福涂料股份有限公司 water-based paint composition
CN102220072A (en) * 2011-04-20 2011-10-19 镇江市万源电子有限公司 Special coating material for aluminium strip insulating coating
CN102229276A (en) * 2011-04-20 2011-11-02 镇江市万源电子有限公司 Aluminum strip with insulation coatings
CN102220072B (en) * 2011-04-20 2015-09-09 镇江市万源电子有限公司 Special coating material for aluminium strip insulating coating
CN103980449A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 Composite material for 3D printing and preparation method thereof
CN108084391A (en) * 2016-11-21 2018-05-29 航天特种材料及工艺技术研究所 A kind of polyurethane and preparation method thereof

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